Polymerization process



perature or below, in an United States Patent 3,131,169 PQLYMERIZATEGNPROCESS Charles J. Norton, Denver, Cola, and Paul N. Rylander, Newark,NJ, assignors to Standard Oil Company, Chicago, EL, a corporation ofIndiana No Drawing. Fiied Nov. 13, 1961, Ser. No. 152,099 12 Claims.(Ci. 26(i-8i$.2)

This invention relates to novel homopolymers and interpolyuners of1,1-dicyclopropylethene and methods for producing the same.

Hitherto it has been known to prepare resinous polymers of olefiniccompounds having a cyclopropyl substituent. Thus, Zones US. 2,540,949and US. 2,540,950 has described certain polymers and copolymers of vinylcyclopropane and of alkyl substituted vinyl cyclopropane. These polymerswere prepared by conventional polymerization processes employingFriedel-Crafts or peroxidetype catalysts. More recently, thepolymerization of vinyl cyclopropane by means of heterogeneous catlaystsof the Ziegler type has been described by Overberger et al., I. Poly.Sci., vol. XLIV, pp. 491-504 (1960).

The present invention is concerned with the preparation of novelresinous materials by the homopolymerization or interpolymeriaztion of1,1-dicyclopropylethene, which may be depicted by the followingstructural formula incorporated in the polymeric chain. Such polymersand copolymers of 1,1-dicyclopropylethene are extremely useful in thatthey may be treated with chemical reagents capable of reacting with thecyclopropyl ring to yield polymeric materials having a variety ofchemically bound side chains. Thus, the polymers of this invention canbe treated with hydrogen bromide, then with an amine or ammonia, andthen neutralized to yield polymers or copolymers containing aminogroups. Such polymeric substances are useful, e.g. as combination VIimprovers and detergents for motor oils.

The reaction of 1,1-dicyclopropylethene to produce polymeric materialsof high molecular weight can be effected by any one of a number ofmethods known per se to the art. For example, 1,1-dicyclopropylethenecan be polymerized by means of acid-reacting catalysts of theFriedel-Crafts type. In effecting such reactions, polymerization isgenerally conducted at temperatures between about -100 C. and 100 0.,preferably at room teminert reaction medium which serves as a solventfor the catalyst. Suitable reaction media which have been employed forthis purpose are benzene, toluene, xylene, solvent naphtha, petroleumnaphtha, carbon tetrachloride, ethylene dichloride, simple alkanehydrocarbons such as ethane, propane, hexane, etc. Among the catalystswhich can be employed are the acidacting metallic halides, e.g. aluminumchloride, aluminum bromide, titanium tetrachloride, stannous chloride,zinc chloride, boron trifiuoride, ferric chloride, or knownorgano-solvent complexes of these metallic halides. Gen- "ice erally,polymerization is effected in the presence of from 0.1% to about 10% byweight of such metal halide catalysts based on the weight of monomericreactant, and polymerization effected over a period of time sufficientto convert all of the reactant to polymer, usually from about one hourto about 24 hours being suflicient. At the conclusion of thepolymerization reaction, the catalyst can be destroyed by addition ofammonia, alcohol, ether or the like, and the polymeric productrecovered.

The use of acid-reacting catalysts of the Friedel-Crafts type permits ofthe preparation of copolymers of 1,1-dicyclopropylethene with tertiaryolefins having from 4 to 10 carbon atoms in the molecule, such asisobutylene, Z-methylpentene-l, 2-ethylpentene-1, Z-methylhexene-l, andthe like. Such comonomers conform to the general structural formula R GCR where each R is an alkyl group and each R is hydrogen or any alkylgroup. In preparing copolymers of this type, it is preferable to employfrom about 1 to 200 mols, preferably between about 10 and mols, oftertiary olefin per mol of l,1-dicyclo propylethene.

We have further found that the polymerization or interpolymerization ofl, l-dicyclopropylethene is not limited to the use of acid-reactingcatalysts, but that this monomer can be effectively polymerized withperioxide-type catalysts, in bulk or aqueous reaction medium, in amanner well known to the art for the polymerization of styrene. The useof peroxide catalysts is particularly effective in the preparation ofcopolymers of 1,1-dicyclopropylethene with monomers such as styrene,vinyl naphthalene, vinyl toluene, vinyl chlcrobenzene, low-boilingconjugated diolefins such as 1,3-butadiene, isoprene, chloroprene, etc.copolymers containing from 0.1 to 10 parts 1,1-dicyclopropylethene perpart of comonomeric material are readily prepared by carrying out thepolymerization in aqueous emulsion under conditions similar to thosewell known in the art.

In such peroxide promoted polymerizations, it is preferred to employreaction temperatures between about 50 and 100 C., using catalystshaving oxidizing characteristics such as have been previously used forthe production of polystyrene. Among such catalysts are the organicperoxides including materials such as benzoyl peroxide, potassiumpersulfate, tert-butyl hydroperoxide or an azo compound such as alpha,alpha'-azodiisobutyronitrile. Usually, it is desirable to use a catalystwhich is soluble in the polymerization medium. Thus, in an aqueousmedium, hydrogen peroxide, sodium percarbonate, sodium perborate or theother alkali metal salts of a peroxy acid may be used. In a non-aqueoussystem, peroxides such as benzoyl peroxide, acetyl peroxide or otherorganic peroxidic compounds may be required.

The polymerization or interpolymerization of 1,1-dicyclopropylethene canbe effected not only with the acidreacting catalysts and peroxide-typecatalysts hitherto mentioned, but equally well with heterogeneouscatalysts of the so-called Ziegler type. These actalysts essentiallycomprise salt-like compounds of groups IVa-Vla of the periodic system,together with metals, metal hydrides or metallo-organic compounds ofgroups I, II or III of the periodic table. Typical catalysts of thistype include titanium halides such as titanium tetrachloride, titaniumtrichloride, vanadium chloride, vanadium oxychloride, etc. together withmetal alkyls such as the aluminum alkyls, e.g. aluminum triethyl,aluminum sesquihalides, and the like, metal hydrides, etc. The artconcerning these catalysts is now highly developed and need not bereproduced here in detail. It is known, for example, that polymerizationwith these catalysts must be effected under anhydrous conditions,generally in inert hydrocarbon reaction media, and at temperatures ofabout room temperaemployed in accordance with the present invention, toproduce the novel polymers of this invention.

PREPARATION OF DICYCLOPROPYLMETHYL- CARBINOL A solution ofmethylmagnesium iodide in ether was prepared from 84 g. (3.5 moles)magnesium turnings, 497 g. (3.5 moles) methyl iodide and 1.1 ofanhydrous ether. The Grignard reagent was cooled in an ice bath and asolution of 330 g. (3 moles) dicyclopropylketone in 300 ml. ether wasadded over a period of one hour. The mixture was stirred overnight atroom temperature. The addition complex was then cooled in an ice bathand 600 ml. cold water was slowly added. (Water is the only safe reagentto use for hydrolysis because acids and even NH Cl cause alcohols ofthis type to rearrange.) The clear ether solution was decanted from themagnesium salt. The salt was extracted several times with ether. Thecombined extracts and ether solution were dried over Drierite. After theether was removed, the product was distilled in vacuo. There wasobtained 270 g. (72% yield) of dicyclopropylmethylcarbinol (3), boilingpoint 56-57 C./10 min, 11 1.4629.

PREPARATION OF 1,1-DICYCLOPROPYLETHENE To 200 g. ofdicyclopropylmethylcarbinol cooled in an ice bath was slowly added withstirring 100 drops of concentrated H 80 The mixture was slowly distilledat 10 mm. pressure. A mixture of H plus organic material which distilledover between 40 and 70 C. was collected. The organic layer Was driedover anhydrous MgSO and distilled in vacuo. There was obtained 132 g. ofdicyclopropylethene, boiling point 4748 C./ 33 mm., n 1.4652.

Analysis.Calc. for C ll C, 88.9; H, 11.1. C, 88.7; H, 11.5.

Oxidation of some of the olefin with neutral aqueous KMnQ; yieldeddicyclopropylketone, which was identified by comparison of the infraredspectra and physical properties of the oxidation product with autheticdicyclopropylketone.

Found:

Example 1 A 50 ml. round-bottom flask equipped with magnetic stirrer wascharged with ml. n-heptane, 10 ml. 1,1-dicyclopropylethene, and 2 ml.1.2 molar Al(i-C H in heptane. Two ml. of a heptane solution 0.3 molarin TiCl was slowly added with stirring over a period of several minutes.Heat was evolved and the mixture became quite viscous and gelled shortlyafter the last of the TiCL; had been added. The mixture was allowed tostand overnight and then mixed with 50 ml. CH OH to yield agrayish-white doughy polymer. The polymer was washed several times withCH OH and boiled with 150 ml. xylene and filtered hot. The material onthe filter Was practically transparent and swelled when placed inxylene. When this translucent polymer was treated with CH OH, thepolymer shrunk somewhat and became pale yellow in color; however, noneof the common solvents would dissolve this polymer. This insolublepolymer was dried in vacuo (10-20 mm.) at 7080 C. for 16 hours. Thedried polymer was hard and somewhat brittle and Weighed about 7 g. Theinfrared spectrum showed the presence of cyclopropyl groups.

The xylene filtrate from the originalwork-up was concentrated byevaporation, cooled, and poured into CH OH whereupon a gummy, paleyellow polymer precipitated. The solvent was decanted and the polymerwas washed With several portions of CH OH. This treatment made thepolymer much firmer. The polymer was dried in vacuo (10-20 mm.) at 70-80C. for 16 hours. The dried hard polymer weighed 2 g. Infrared datashowed that this polymer contained cyclopropyl groups.

X-ray data indicated that both of these polymers were non-crystalline.

Example 2 A 50 ml. round-bottom flask was charged with 7 ml. n-heptaneand 5 ml. 1,1-dicyclopropylethene. One ml. of 0.3 molar TiCL; in heptanewas added dropwise to the olefin solution. The mixture was stirred overnight at room temperature and then poured into 100 ml. CHgOH, whereupona white gummy polymer precipitated. The polymer was dissolved in boilingxylene. The solution was filtered hot and filtrate was concentrated,cooled, and poured into CI'IgOH, whereupon a gummy polymer precipitated.The polymer was washed several times with CH OH and dried at C. and 15mm. pressure for 16 hours. The infrared spectrum of the polymer showedstrong cyclopropane absorption indicating that the cyclopropane ringremained intact during the polymerization.

Example 3 500 ml. 3-116Ck, round-bottom flask equipped with stirrer,condenser, and thermometer and cooled in a Dry- Ice bath was chargedwith 95 ml. condenser isobutylene and 3 g. 1,1-dicyclopropylethene. Thetemperature was maintained at 50 to 40 F. while a solution of 6 ml. TiClin 15 ml. pentane was added in 2 ml. portions. After about 15 minutes,the mixture was extremely viscous. The doughy mass was transferred to abeaker containing 400 ml. CH OH, whereupon a white gummy polymerdeveloped. The copolymer was dissolved in hot hexane and reprecipitatedby pouring the hexane solution into CH OH. The copolymer was then washedwith CH OH and dried in a vacuum oven at 75 C. for 12 hours. Comparisonof the infrared spectra of the copolymer and pure polyisobutylene showedthat the two Were difierent and the copolymer spectrum showed theExample 4 A Fisher-Porter tube was charged with 20 g. benzene, 2 g.1,1-dicyclopropylethene, 18 g. freshly distilled styrene, and 0.2 g.benzoyl peroxide. The tube was sealed and heated at -100 C. for 22hours. The mixture was cooled and poured into 300 ml. CH OH, whereupon awhite gummy polymer precipitated. The copolymer was dissolved in hotbenzene and reprecipitated by pouring into CH OH. The copolymer whichwas dried in a vacuum oven at 75 C. for 18 hours had the appearance ofpolystyrene.

The polymers and interpolymers of the present invention are highmolecular weight, resinous materials having utility for the fabricationof molded, extruded or cast articles, and for the formation of film.They may be fabricated into articles for which conventional polymerssuch as polyethylene and polystyrene have hitherto been employed. Thepolymers and interpolymers may be blended with other thermoplasticpolymers; or compounded with fillers, foaming agents and the like toserve particular applications. The polymers and interpolymers of1,1-dicyclopropylethene are particularly valuable since the threemembered rings thereof provide points of chemical reaction by which awide variety of substituted linear polymers can be prepared. Thus, thecyclopropyl polymers can be treated with acidic materials to isomerizethe three-membered ring to a propenyl or isopropenyl group. Thisolefinic group may then be further modified with chemical reagents tointroduce various functional groups or may be further polymerized orcopolymerized to give a higher molecular weight polymer-linear orcrosslinked.

Having described our invention, what we claim is:

1. Poly-(1,1-dicyclopropy1ethene).

2. As a new composition of matter, an interpolymer of1,1-dicyclopropylethene and a tertiary olefin having the formula R C=CRwherein each R is an alkyl group and each R is selected from the groupconsisting of hydrogen and alkyl, said olefin having from 4 to 10 carbonatoms in the molecule.

3. As a new composition of matter, an interpolymer of1,1-dicyclopropylethene and isohutylene.

4. As a new composition of matter, an interpolymer of1,1-dicyclopropylethene and styrene.

5. A process for producing high molecular weight materials whichcomprises polymerizing 1,1-dicyclopropylethene in the presence of aFriedel-Crafts catalyst in an inert liquid reaction medium.

6. A process for producing high molecular weight materials whichcomprises inter-polymerizing Ll-dicyclopropylethene and an olefin offrom 4 to 10 carbon atoms having the structural formula R C CR whereineach R is an alkyl group and each R is selected from the groupconsisting of hydrogen and alkyl in the presence of a Friedel-Craftscatalyst in an inert liquid reaction medium.

7. The process of claim 6 wherein said olefin is isobutylene.

8. The process of claim 6 wherein said Friedel-Crafts catalyst is TiCl9. A process for producing high molecular weight materials whichcomprises polymerizing 1,1-dicyclopropylethene in the presence of aperoxide polymerization catalyst.

10. The process of claim 9 wherein said polymerization is effected inthe presence of styrene.

11. A process for producing high molecular weight materials whichcomprises polymerizing 1,1-dicyclopropylethene in the presence of acatalyst comprising a salt-like compound of a metal of groups IVa, Va,and VIa with a member of the group consisting of groups I, II and IIImetals, metal hydrides and metallo organic compounds.

12. The process of claim 11 wherein the catalyst is TiCl; and aluminumtriisobutyl.

No references cited.

1. POLY-(1,1-DICYCLOPROPYLETHENE).
 2. AS A NEW COMPOSITION OF MATTER, ANINTERPOLYMER OF 1,1-DICYCLOPROPYLETHENE AND A TERTIARY OLEFIN HAVING THEFORMULA R2C=CR''2 WHEREIN EACH R IS AN ALKYL GROUP AND EACH R'' ISSELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND ALKYL, SAID OLEFINHAVING FROM 4 TO 10 CARBON ATOMS IN THE MOLECULE.